Ring-Opening Polymerization of Epoxides: Facile Pathway to Functional Polyethers via a Versatile Organoaluminum Initiator

• Published in: Macromolecules Vol. 50; no. 8; pp. 3121 - 3130
• Main Authors: Rodriguez, Christina G, Ferrier, Robert C, Helenic, Alysha, Lynd, Nathaniel A
• Format: Journal Article
• Language: English
• Published: American Chemical Society 25-04-2017
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/acs.macromol.7b00196

We report a new class of organoaluminum-based initiator for anionic ring-opening polymerization of epoxides that is simple to synthesize from readily available precursors. The resultant organometallic initiator was the triethyl­aluminum adduct of (2-dibenzyl­amino)­ethoxy­diethylaluminum (TAxEDA) [(AlEt3)·(O­(AlEt2)­CH2­CH2N­(Bn)2)], which was isolated by direct crystallization from the reaction medium and then compositionally and structurally characterized by NMR spectroscopy and XRD. We studied the reactivity and versatility of the new initiator through the polymerization of propylene oxide, butylene oxide, epichlorohydrin, and allyl glycidyl ether into homopolymer, statistical copolymer, and block copolymer architectures with heterobifunctional end-groups consisting of dibenzylamine and hydroxyl functionalities. The TAxEDA-initiated polymerizations were consistent with a controlled, living, anionic mechanism that was tolerant of chemical functionality and exhibited no chain transfer to monomer that limits the traditional anionic ring-opening polymerization of substituted epoxides.